Stabilization of organic substances



United States Patent 3,316,175 STABILIZATION OF ORGANIC SUBSTANCES EdwinJ. Latos, Chicago, and Charles M. Hayes, Hoffman Estates, 11].,assignors to Universal Oil Products ompany, Des Plaines, 11]., acorporation of Delaware 0 Drawing. Original application Dec. 12, 1963,Ser. No. 330,008. Divided and this application Dec. 10, 1965, Ser. No.513,079

10 Claims. (Cl. 252-325) This application is a division of co-pendingapplication Ser. No. 330,008, filed Dec. 12, 1963, and relates to thestabilization of organic substrates by incorporating therein a novelcomposition of matter comprising the reaction product of a particulartype of dicarboxylic acid or anhydride thereof, amine and phosphate orthiophosphate, and to the use of the resultant reaction product.

As will be set forth in detail hereinafter, the reaction product of thepresent invention is particularly useful as an additive to lubricatingcompositions comprising a major proportion of an oil of lubricatingviscosity. A specific example of such a lubricating composition is E.P.(extreme pressure) lubricating oil used, for example, in the lubricationof hypoid gears, in which service the oil must meet the severerequirements of high torquelow speed, low torque-high speed and hightorque-high speed conditions. These requirements are even more severebecause such oils must perform satisfactorily for long periods of timewhich may be as high as 100,000 miles or more and even for the life ofthe vehicle.

As hereinbefore set forth, a novel composition of matter of the presentinvention is prepared by the reaction of a particular type ofdicarboxylic acid or anhydride, amine and phosphate. The particular typeof acid or anhydride is a polyhalopolyhydropolycyclicdicarboxylic acidor anhydride thereof. Any suitable acid or anhydridemeeting theserequirements is used in accordance with the present invention. In oneembodiment the acid or anhydride is of the type known in the art asChlorendie or HET acid or anhydride. This acid is preprod by theDiels-Alder addition reaction of maleic acid andhexachlorocyclopentadiene, the latter also being referred to in the artas Hexachlor. The corresponding anhydride is prepared by the reaction ofmaleic anhydride and hexachlorocyclopentadiene. This acid or anhydridealso may be named l,4,5,6,7,7-hexachlorodicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid or the corresponding anhydride. Thesecompounds are prepared by the reactionof equal molar quantities of thereactants, generally by refluxing in the presence of a solvent. are wellknown in the art and are described, for example, in US. Patent 2,606,910and elsewhere.

In place of maleic acid or maleic anhydride, it is understood that othersuitable dicarboxylic acids containing carbon to carbon unsaturation maybe employed. Illustrative examples include fumaric acid, itaconic acid,citraconic acid, glutaconic acid, etc. Also, in place of hexachlorocyclopentadiene, other suitable halo-substitutedcycloalkadienes'may be used. Illustrative examples include1,Z-dichlorocyclopentadiene, 1,5-dichlorocyclopentadiene,l,2,3-trichlorocyclopentadiene, 1,2,3,4-tetrachlorocyclopentadiene,1,2,3,4,5 pentachlorocyclopentadiene and similar compounds in which allor part of the chlorine is replaced by other halogen and particularlybromine.

A particularly preferred polyhalopolyhydropolycyclicdicarboxylic acid oranhydride is prepared by the Diels- Alder condensation of a conjugatedaliphatic diene with an olefinic dicarboxylic acid and then furthercondensing the resultant cyclohexenedicarboxylic acid with ahalocycloalkadiene. A particularly preferred reaction product is theDiels-Alder condensation of 1,3-butadiene with maleic acid to form1,2,3,6-tetrahydrophtha1ic acid, fol- These reactions lowed by theDiels-Alder condensation with hexachlorocyclopentadiene. hexachloro1,2,3,4,4a,5,8,8a octahydro 5,8 methano- 2,3-naphthalenedicarboxylicacid, hereinafter referred to as A acid. The corresponding anhydride isprepared starting with maleic anhydride instead of maleic acid. Theanhydride may 'be named 5,6,7,8,9,9-hexachloro- 1,2,3,4,4a,5,8,8aoctahydro 5,8 methano 2,3 naphthalenedicarboxylic anhydride, hereinafterreferred to as A anhydride. Here again, other conjugated aliphaticdienes may be used including, for example, 2-rnethyl-l,3- butadiene,1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene,2,3-dimethyl-1,3-butadiene, 1,3-heptadiene, 2,4-heptadiene, conjugatedoctadienes, conjugated nonadienes, etc., halodienes as, for example,chloroprene and particularly I-chlorobutadiene and1,4-dichlorobutadiene. Similarly, other unsaturated dicarboxylic acidsmay be used including fumaric acid, itaconic acid, citraconic acid,glutaconic acid, mesaconic acid, etc. Also, other halocycloalkadionesmay be used including, for example, those specifically hereinbefore setforth. The preparation of these compounds also is known in the art andis set forth in detail in US. Patent 3,017,431.

Still another preferred polyhalopolyhydropolycyclicdicarboxylic acid oranhydride is prepared by condensing cyclopentadiene with maleic acid ormaleic anhydride to form norborn-5-ene-2,3-dicarboxylic acid oranhydride same with hexachloropentadiene. The product may be namedL5,6,7,8,'9,9,-hexachlorol,2,3,4,4a,5,8,8a octahydro 1,4,5,8 dimethano2,3- naphthalenedicarboxylic acid or anhydride, hereinafter referred toas B acid and B anhydride respectively. Here again, it is understoodthat other conjugated cycloaliphatic clienes, other unsaturateddicarboxylic acids or anhydrides and other polyhalocycloalkadienes maybe used to prepare suitable polyhalopo lyhydropolycyclicdicarboxylicacids or anhydrides.

From the above, it Will be seen that any suitablepolyhalopolyhydropolycyclicdicarboxylic acid or anhydride may be used inaccordance with the present invention. Thepolyhalopolyhydrop-olycyclicdicarboxylic acid may be illustrated by thefollowing general structure:

in which X is selected from the group consisting of halogen andparticularly chlorine and/or bromine, hydrogen and an alkyl radical offrom one to ten and preferably from one to four carbon atoms, at leasttwo of the Xs being halogen, Y is selected from the group consisting ofhalogen, hydrogen and an alkyl radical of one to ten and preferably fromone to four carbon atoms, In is an integer of from one to four, n rangesfrom zero to four and p ranges from zero to four.

The above structure illustrates the dicarboxylic acid. In the interestof simplicity, the corresponding anhydride is not being illustrated, butis readily ascertainable from the above structure.

Referring to the above structure, when X is chlorine, m is one, It iszero and p is zero, the compound is l,4,5,6,7,7-hexachloro-(2.2.1)5-heptene-2,3-dicarboxylic acid or the corresponding anhydride.Similarly, when X is chlorine, m is one, It is zero and p is one, thecompound is5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylicacid or the corresponding anhydride. Also, when X is chlorine, Y is Theproduct may be named 5,6,7,8,9,9-

hydrogen, m is one, n is one and p is one, the compound is 5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8a octahydro-1,4,5,8-dimethano-2,3-naphthalenedicarboxylic acid or the correspondinganhydride. I

The particular type of amine for reaction with the acid or anhydrideheretofore described is a polyamine. For the reasons to be hereinafterset forth it is an essential feature of the present invention that theamine contains at least two amino groups. The amino groups may beprimary, secondary and/or tertiary. In one embodiment at least one aminogroup is a primary or secondary amine and the other amino group orgroups may be primary, secondary or tertiary. In another embodiment bothamino groups of the diamine may be tertiary amines. Any suitable aminemeeting the above requirements may be used in accordance with thepresent invention.

In one embodiment the amine is an alkylene polyamine. Illustrativealkylene polyamines include ethylenediamine, propylenediamine,butylenediamine, .pentylenediamine, hexylenediamine, etc.,diethylenetriamine, dipropylenetriamine, dibutylenetriamine,dipentylenetriamine, dihexylenetriamine, etc., triethylenetetraamine,tripropylenetetraamine, tributylenetetraamine, tripentylenetetraamine,trihexylenetetraamine, etc., as well as the alkylene polyamines in whichone or more of the nitrogen atoms contain alkyl substituents, the alkylsubstituent or substituents being selected from methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl, eicosyl, etc. Illustrative amines in this embodiment includeN-alkylethylenediamine, N,N'-dialkyl-ethylenediamine, similar-1ysubstituted propylenediamine, butylenediamine, pentylenediamine,hexylenediamine, etc., N-alkyl-diethylenetriamine, N ,N dialkyldiethylenetriame, N ,N ,N trialky l-diethylenetriamine, similarlysubstituted dipropylenetriamine, dibutylenetriamine,dipentylenetriamine, dihexylenetriamine, etc.,N-alkyl-triethylenetetramine, N ,N -dialkyl-triethylenetetraamine, N ,N,N trialkyl triethylenetetraamine, N ,N ,N ,N tetraalkyltriethylenetetraamine, similarly substituted tripropylenetetraamine,tributylenetetraamine, tripentylenetetraamine, trihexyleneteraamine,etc. It is understood that the alkyl groups will be selected from thosehereinbefore set forth.

In another embodiment the diamines are N-alkyldiaminoalkanes. Aparticularly preferred amine of this class comprises an N;alkyl.-1,3-diaminopropane in which the alkyl group contains from abouteight to about twentyfive carbon atoms. A number ofN-alkyl-diaminoalkanes of this class are available commercially, such asDuomeen T" and Diam 26 in which the alkyl group is derived from tallowand contians from about twelve to about twenty carbon atoms per groups,and mostly sixteen to eighteen carbon atoms. OtherN-alkyl1,3-diaminopropanes may be prepared to contain any number ofcarbon atoms desired in the alkyl group and thus the alkyl group isselected from methyl, ethyl, propyl, butyl, pentyl, hexy-l, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexade-cyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.

While the N-alkyl-l,3-diarninopropanes are preferred, it is understoodthat other suitable N-alkyl-diaminoal kanes may be employed.Illustrative examples include N-alkyl-l,2-diaminoethane,N-alkyl-1,2-diaminobutane,

etc.

In another embodiment the amine is an aromatic diamine. Illustrativeexamples include ortho-, metaand particularly para-phenylenediamines, aswell as the N-alkylated and/ or N,N-dialkylated phenylenediamines inwhich the alkyl group or groups contain from one to twelve or morecarbon atoms. Other aromatic amines include diaminodiphenyl alkanes inwhich the alkane group contains from one to six or more carbon atoms,diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl amine,as Well as the diaminodiphenyl compounds in which one or both of theamino groups are substituted with an alkyl radical of from one tosixteen or more carbon atoms each. It is understood that a mixture ofthe aliphatic polyamines and/or of the aromatic polyamines may be usedfor reaction with the acid or anhydride hereinbefore set forth.

The reaction of the acid or anhydride with the polyamine is effected inany suitable manner. The polyamine will be selected with particularregard to the acid or anhydride with which it is to be reacted. Forexample, when the HET acid or anhydride is to be used, the polyamineshould be a highly alkylated polyamine. For example, preferred diaminesfor reaction with the HET acid or anhydride include Duomeen T or Diam 26or other highly alkylated diamines. On the other hand, when using the Aacid or A anhydride, a stronger polyamine may be used includingethylenedia-mine, diethylenetriamine, etc.

The specific conditions for reacting the acid or anhydride and polyaminewill depend upon whether the reaction product is to be a salt orneutralization product formed under conditions which avoid theliberation of water or whether the reaction product is to be formed withthe liberation of water. When the reaction product is to be a salt, thepolyamine may comprise primary, secondary and/ or tertiary amine groups.When the mono or half salt is desired, the reactants are reacted in anequal mole proportion of acid and polyamine. When the double salt isdesired, the reactants are reacted in a proportion of one mole of acidand two moles of polyamine. However, when desired, an excess of one ofthe reactants may be used. The acid is used for the preparation of thesalt. When the anhydride is to be used, it first should be hydrolyzed toform the acid for subsequent preparation of the salt.

As hereinbefore set forth, the formation of the salt is effected undermild conditions and conveniently is effected by intimately mixing thereactants at ambient temperature (about 10 to about 32 C.), although anelevated temperature which generally will not exceed about 70 C. may beemployed, particularlywhen the reaction is effected undersuperatmospheric pressure which may range from 5 to 500 pounds persquare inch or more. The time of mixing will be sufiicient to effectsubstantially complete reaction and may vary from about 0.25 to 12 hoursor more. The reaction is readily effected by intimately mixing thereactants, preferably in the presence of a suitable solvent. The solventis used to facilitate dissolving the reactants and particularly the acidand thereby forming a readily reactable solution. Either one or both ofthe reactants may be prepared as separate solutions in the solvent andthe reactants then are intimately mixed. Any suitable solvent may beused and, in one embodiment, preferably comprises an aromatichydrocarbon including benzene, toluene, xylene, ethylben zene, cumene,etc., or a mixture thereof. In another em bodiment the solvent comprisesa paraffinic hydrocarbon including pentane, hexane, heptane, octane,nonane, decane or a mixture thereof. In another embodiment the solventcomprises an ether and particularly ethyl ether. It is understood thatany suitable solvent in which the reactants are soluble and which isinert under these conditionsmay be employed. In most cases the solutionof the salt in the solvent Will be used as such in the next step of theprocess. However, when desired, the solvent may be removed from the saltin any suitable manner.

When the reaction of the acid or anhydride and a or more carbon atoms.

amine is elf ected with the liberation of water, the reactants arereacted in a ratio of one mole proportion of acid and from one to twomole proportions of plyamine and equal mole proportions of anhydride andpolyamine.

Here again, an excess of one of the reactants may be employed whendesired. In order to favor the mole for mole reaction product, an excessof the polyamine preferably is used and this excess may range up totenor more mole proportions of polyamine per one mole proportion of theanhydride. One or both of the reactants are conveniently prepared as asolution in a solvent, which solvent conveniently is selected from thosehereinbefore specifically set forth. The reactants then are commingledand heated to refluxing conditions to cause interaction of the acid oranhydride and the polyamine, with the liberation of water. The refluxtemperature will depend upon the particular solvent used and generallywill be within the range of from about 80 to about 250 C. When desired,the reaction is effected under superatmospheric pressure which may bewithin the range of from 5 to 500 pounds per square inch or more. Thetime of refluxing generally will range from about 0.5 to 12 hours ormore. The water formed during the reaction preferably is continuouslyremoved from the reaction zone. In the preparation of the reactionproduct accompanied by the liberation of water, it is believed that thereaction product is an irm'de-amine. In one embodiment this product isrecovered in admixture with the solvent and may be used as such for thenext step of the process. However, when desired, the solvent may beremoved in any suitable manner, including distillation under atmosphericor subatmospheric pressure to recover the intermediate product free ofsolvent.

The reaction product of the acid or anhydride and amine is reacted toform-the phosphate salt. While phosphoric acid may be used, preferablyan alkyl phosphate is employed. Any suitable alkyl phosphate is used andincludes both the alkyl acid orthophosphates and the alkyl acidpyrophosphates. In the alkyl acid orthophosphates, the monoalkyl ester,dialkyl ester or a mixture thereof may be employed. In the alkyl acidpyrophosphates, the monoalkyl 'ester, dialkyl ester, trialkyl ester ormixtures thereof may be employed, the dialykyl esters being preferredand the ester groups may be attached to the same or different phosphorusatom. Generally, however, this compound will be symmetrical and,accordingly, the alkyl ester groups will be attached to differentphosphorus atoms.

In a preferred embodiment the alkyl phosphate contains at least onealkyl group of at least six carbon atoms and more particularly fromabout six to about twenty illustrative preferred alkyl acidorthophosphates include monohexyl acid orthophosphate, dihexyl acidorthophosphate, mixture of monoand di hexyl acid orthophosphates,monoheptyl acid orthophosphate, diheptyl acid orthophosphate, mixture ofmonoand diheptyl acid orthophates, monooctyl acid orthophosphate,dioctyl acid orthophosphate, mixture of monoand dioctyl acidorthophosphates, monononyl acid orthophosphate, dinonyl acidorthophosphate, mixture ofmonoanddinonyl acid orthophosphates, monodecylacid orthophosphate, didecyl acid orthophosphate, mixture of monoanddidecyl acid orthophosphates, monoundecyl acid orthophosphate, diundecylacid orthophosphate, mixture of monoand diundecyl acid orthophosphates,monododecyl acid orthophosphate, didodecyl acid orthophosphate, mixtureof monoand didodecyl acid orthophosphates, monotridecyl acidorthophosphate, ditridecyl acid orthophosphate, mixture of monoandditridecyl acid orthophosphates, monotetradecyl acid orthophosphate,ditetradecyl acid orthophospate, mixture of monoand ditetradecyl acidorthophosphates, monopeutadecyl acid orthophosphate, dipentadecyl acidorthophosphate, mi."- ture of -monoand dipentadecyl acidorthophosphates, monononadecyl acid orthophosphate, dinonadecyl acid.cosyl acid orthophosphates, etc.

orthophosphate, mixture of monoand dihexadecyl acid orthophosphates,monoheptadecyl acid orthophosphate, diheptadecyl acid orthophosphate,mixture of monoand diheptadecyl acid orthophosphates, monooctadecyl acidorthophosphate, dioctadecyl acid orthophosphates, mixture of monoanddioctadecyl acid orthophosphates, monononadecyl acid orthophosphate,dinonadecyl acid orthophosphate, mixture of monoand dinonadecyl acidorthophosphates, monoeicosyl acid orthophosphate, dieicosyl acidorthophosphate, mixture of monoand diei- In another embodiment the alkylgroup or groups are selected from methyl, ethyl, propyl, butyl andpentyl. It is understood that a mixture of the phosphates having alkylgroups of'different chain lengths may be employed.

Preferred alkyl acid. pyrophosphates include monohexyl acidpyrophosphate, dihexyl acid pyrophosphate, mixture of monoand dihexylacid pyrophosphates, monoheptyl acid pyrophosphate, diheptyl acidpyrophosphate,

mixture of monoand diheptyl acid pyrophosphates,

'monononyl acid pyrophosphate, dinonyl acid pyrophosphate, mixture ofmonoand dioctyl acid pyrophosphates, moononyl acid pyrophosphate,dinonyl acid pyrophosphate, mixture of monoand dinonyl acidpyrophosphates,

monodecyl acid pyrophosphate, didecyl acidpyrophosphate, mixture ofmonoand didecyl acid pyrophosphates,

monoundecyl acid pyrophosphate, diundecyl acid pyrophospate, mixture ofmonoand diundecyl acid pyrophosphates, monododecyl acid pyrophosphate,didodecyl acid pyrophosphate, mixture of monoand didodecyl acidpyrophosphates, monotridecyl acid pyrophosphate, ditridecyl acidpyrophosphate, mixture of monoand ditridecyl acid pyrophosphates,monotetradecyl acid pyrophosphate, ditetradecyl acid pyrophosphate,mixture of monoand ditetradecyl acid pyrophosphates, .monopentadecylacid pyrophosphate, dipentadecyl acid pyrophosphate, mixture of monoanddipentadecyl acid pyrophosphates, monohexadecyl acid pyrophosphate,dihexadecyl acid pyrophosphate, mixture of monoand dihexadecyl acidpyrophos phates, monoheptadecyl acid pyrophosphate, diheptadecyl acidpyrophosphate, mixture of monoand diheptadecyl acid pyrophosphates,monooctadecyl acid pyrophosphate, dioctadecyl acid pyrophosphate,mixture of monoand dioctadecyl acid pyrophosphates, monononadecyl acidpyrophosphate, dinonadecyl acid pyrophosphate, mixture of monoanddinonadecyl acid pyrophosphates, monoeicosyl acid pyrophosphate,dieicosyl acid pyrophosphate, mixture of monoand dieicosyl acidpyrophosphates, etc. In another embodiment the alkyl group or groups areselected from methyl, ethyl, propyl, butyl and pentyl. It is understoodthat a mixture of the phosphates having alkyl groups of difierent chainlengths may be employed.

Another phosphate for reaction with the acid or anhydride and polyaminereaction product is prepared by the oxyalkylenation of an alcohol, whichmay be of aliphatic or aromatic con-figuration, and then forming thephosphate thereof. Aliphatic alcohols for oxyalkylenation may besaturated or unsaturated and preferably contain at least four carbonatoms and more prticularly from about six to twenty or more carbonatoms. Illustrative alcohols include butyl alcohol, pentyl alcohol,hexyl alcohol, heptyl -alcohol,-octyl alcohol, nonyl alcohol, decylalcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecylalcohol, pentadecyl alcohol, hcxadecyl alcohol, heptadecyl alcohol,octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, etc. Thesealcohols conveniently are derived from fatty acids and accordinglyinclude, for example, lauryl alcohol, myristyl alcohol, palmitylalcohol, stearyl alcohol, decylenyl alcohol, dodecylenyl alcohol,palrnitoleyl alcohol, oleyl alcohol, linoleyl alcohol, linolenylalcohol, gadoleyl alcohol, etc. Aromatic alcohols include phenol andparticularly alkylphenols. The alkylphenols preferably contain at leastfour and more particularly from about six to about twenty carbon atomsin the alkyl group. Illustrative alkylphenols include hexylphenolheptylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol,dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol,hexadecylphen-ol, heptadecylphenol, octadecylphenol, nonadecylphenol,eicosylphenol, etc., as well as dialkyl and trialkylphenols in which thealkyl groups are selected from those hereinbefore specifically setforth. Also, the polyalkylphenols may contain one or more alkyl groupscontaining from one to six carbon atoms and one or more alkyl groupscontaining from six to twenty carbon atoms.

Oxyalkylenation of the aliphatic or aromatic alcohol is eifected in anysuitable manner. While ethylene oxide is preferred for reaction with thealiphatic or aromatic alcohol, it is understood that propylene oxide,butylene oxide, pentylene oxide, hexylene oxide, etc., may be used. Theoxyalkylenation is eilected by reacting the aliphatic or aromaticalcohol with the alkylene oxide, particularly ethylene oxide, in themolar ratios to produce the oxyalkylenated alcohol or phenol containingthe oxyalkylenated group in the desired proportion. In a preferredembodiment, the oxyalkylenated alcohol or phenol contains-from. two toabout twelve or more and particularly from two to about six oxyalkylenegroups. The oxyalkylenation is efiected in any suitable manner andgenerally will be conducted at a temperature of from ambient to about175 C. and more particularly from about 90? C. to about 150 C.,preferably in the presence of a catalyst such as sodium hydroxide,potassium hydroxide, tertiary amine, quaternary hydroxide, etc. When theoxyalkylenation is to be limited to the addition of one oxy group, thecatalyst is used with the alkanols but may be omitted with thealkylphenols. Superatrnospheric pressure may be employed and may bewithin the range of from about 10 to 1000 pounds or more.

The oxyalkylenated aliphatic or aromatic alcohol then is reacted in anysuitable manner with P to form the desired phosphate. One molarproportion of P 0 or other suitable phosphorus oxide is reacted per oneor two molar proportions of the oxyalkylenated hydrocarbon. In general,an excess of P 0 is employed in order to insure complete reaction. Thereaction is effected at a temperature wit-bin the range of from ambientto about 110 C. and under substantially anhydrous conditions. Theresultant free acid form of the phosphate generally is recovered as aviscous liquid.

Another embodiment of the invention comprises the alkyl thiophosphatesalt of the acid or anhydride-polyamine reaction product. Illustrativepreferred dialkyldithiophosphates include monohexyl-dithiophosphate,dihexyl-dithiophosphate, mixture of monoand dihexyl-dithiophosphate,monoheptyl-dithiophosphate, diheptyl-dithiophosphate, mixture of monoanddiheptyl-dithiophosphate, monooctyl dithiophosphate, dioctyldithiophosphate, mixture of monoand dioctyl-dithiophosphate, monononyldithiophosphate, dinonyl dithiophosphate, mixture of monoanddinonyl-dithiophosphate, monodecyl-dithiophosphate,didecyl-dithiophosphate, mixture of monoand didecyl-dithiophosphate,monoundecyl-dithiophosphate, diundecyl-dithiophosphate, mixture of monoand diundecyl-dithiophosphate, monododecyl-drthiophosphate,didodecyl-dithiophosphate, mixture of monoand didodecyl-dithiophosphate,monotrrdecyl-dithiophosphate, ditridecyl-dithiophosphate, mixture ofmonoand ditridecyl-dithiophosphate, monotetradecyl-drthiophosphate,ditetradecyl-dithiophosphate, mixture of v r 8 monoandditetradecyl-dithiophosphate, monopentadecyldithiophosphate,dipentadecyl-dithiophosphate, mixture of monoanddipentadecyl-dithiophosphate, monohexadecyl dithiophosphate,dihexadecyl-dithiophosphate, mixture of monoanddihexadecyl-dithiophosphate, monoheptadecyldithiophosphate,diheptadecyl-dithiophosphate, mixture of monoanddiheptadecyl-dithiophosphate, monooctadecyh' dithiophosphate,dioctadecyl-dithiophosphate, mixture of monoanddioctadecyl-dithiophosphate, monononadecyldithiophosphate,dinonadecyl-dithiophosphate, mixture of monoanddinonadecyl-dithiophosphate, monoeicosyl-dithiophosphate,dieicosyl-dithiophosphate, mixture of monoand dieicosyl-dithiophosphate,etc. The oxyalkylenated aliphatic or aromatic alcoholdithiophosphatesare prepared in substantially the same manner as hereinbefore set forthfor the oxyalkylenated aliphatic or aromatic alcohol phosphates, exceptthat P 8 or other suitable phosphorus sulfide is used instead of thephosphorus oxide.

The phosphate or thiophosphate salt of the acid or anhydride-polyaminereaction product is prepared in any suitable manner. In general, thephosphate or thiophosphate will be used in a ratio of from one to twomole proportions of phosphate or thiophosphate per one mole proportionof acid or anhydride-amine reaction product.

However, an excess or deficiency of the phosphate 01' thiophosphate maybe employed when desired and thus may be within the range of from about0.5 to about 4 mole proportions of phosphate or thiophosphate per onemole proportion of acid or anhydride-amine reaction product. The salt isprepared in any suitable manner and conveniently by intimately mixingthe acid or anhydride.- polyamine reaction product and the phosphate orthiophosphate at ambient temperature although, here again, an elevatedtemperature may be used which generally will not exceed about C. Themixing may be eifected at atmospheric pressure or, when desired, undersuperatmospheric pressure which may be within the range of from about 5to pounds per square inch or more. Also, when desired, the phosphate orthiophosphate may be prepared as a solution in a suitable solvent andthen commingled with the other reactant. Conveniently, the solvent willbe the same as used in the earlier step of the process.

In general, it is preferred to prepare the reaction product of thepresent invention in the sequence hereinbefore set forth of reacting theacid or anhydride with the amine and then with the phosphate orthiophosphate. In another embodiment the phosphate or thiophosphate maybe re acted with the polyamine to form the phosphate orthiophosphate-polyamine salt and then reacted with the acid oranhydride. In still another embodiment the phosphate or thiophosphatemay be commingled in an oil or other substrate and the acid oranhydride-amine reaction product added thereto to form the phosphatesalt in situ.

Without intending to be limited thereto, it isbelieved that the novelcompositions of matter of the present invention will be of the generalstructures illustrated below. In the interest of simplicity, thestructures shown below are limited to products prepared from a-diamine,it being understood that the structures will' be modified when apolyamine containing three or more nitrogen atoms is used in preparingthe composition of matter. In another embodiment the polyamine is acyclic polyamine and particularly cyclohexyl diamine.

where X, Y, m, n and p have the same designations as hereinbefore setforth, R is selected from the group consisting of an alkylene group offrom two to twenty carbon atoms and an aryl group, R is selected fromthe group consisting of hydrogen and an alkyl group of from one tothirty carbon atoms, R" is selected from the group consisting ofhydrogen, an alkyl group of from one to thirty carbon atoms, anoxyalkylenated aliphatic alcohol and an oxyalkylenated aromatic alcohol,Z is selected from the group consisting of oxygen and sulfur, B isselected from the group consisting of a diamine, a diamine phosphate anda diamine thiophosphate, and q ranges from zero to one.

Referring to structure (1), when q is zero, the composition of matter isthe monoor half salt prepared under conditions which avoid theliberation of water as hereinbefore set forth. When q is one, thecomposition of matter is the'double salt also prepared under conditionswhich avoid the liberation of water. Structure (2) illustrates thereaction product formed under conditions to liberate water and, ashereinbefore set forth, it is believed to be an imide-amine-phosphatesalt.

As hereinbefore set forth, applicants do not intend to be limited to thestructures illustrated above. It is understood that the final productmay contain a mixture of compounds including those formed byintermolecular condensation, polymerization, etc. Because the specificstructure of the final products has not been definitely established,applicants are claiming the composition by the method of manufacture.

Conveniently the final product is recovered as a solution in a suitablesolvent and is used in this manner as an additive to an organicsubstrate. However, when the product is recovered in the absence ofasolvent or when the product is not sufiiciently soluble in thesubstrate, the desired solubility may be obtained by dissolving thereaction product in a mutual solvent. Suitable solvents for this purposecomprise phenols and particularly alkylphenols of polyalkylphenols inwhich the alkyl group contains from six to twenty carbon atoms. Thephenol may be used in a concentration of from about 5% and preferablyfrom about to about 200% by weight, and more particularly from about toabout 100% by Weight of the reaction product of the present invention.

As hereinbefore set forth, the acid or amine phosphate reaction productof the present invention is particularly advantageous for use inlubricating oil and particularly in lubricating oils which must meetsevere requirements. It Will be noted that the reaction product of thepresent invention contains halogen, nitrogen and phosphorus in oneembodiment and also sulfur in another embodiment. Experience has shownthat compounds containing these ele ments are especially advantageousfor use in lubricating oils subject to severe conditions. However, whilethe reaction product of the present invention is especially useful insuch lubricating oils, it is understood that it also is used toadvantage in other lubricating oils. Another advantage of thecompositions of the present invention is that certain of thesecompositions will not cause during use.

The lubricating oil may be of natural or synthetic origin. The mineraloils include those of petroleum origin and are referred to as motorlubricating oil, railroad type lubricating oil, marine oil, transformeroil, turbine oil, ditferential oil, diesel lubricating oil, gear oil,cylinder oil, specialty darkening of the oil products oils, etc. Othernatural oils include those of animal, marine or vegetable origin.

Synthetic lubricating oils are of varied types including aliphaticesters, polyalkylene oxides, silicones, esters of phosphoric and silicicacids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic:esters, di-(Z-ethylhexyl) sebacate is being used in a comparativelylarge commercial scale. Other aliphatic esters include dialkyl azelates,dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkylglutarates, etc. Specific examples of these esters include dihexylazelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate,di-3,5,5-trimethylpentyl glutarate, di-(Z-ethylhexyl)-pimelate,di-(Z-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritoltetracaproate, dipropylene glycol dipelargonate, l,5-pentanediol-di-(Z-ethylhexanonate), etc. The polyalkylene oxides includepolyisopropylene oxide, polyisopropylene oxide diether, polyisopropyleneoxide diester, etc. The silicones include methyl silicone, methylphenylsilicone, etc., and the silicates include, for example, tetraisooctylsilicate, etc. The highly fluorinated hydrocarbons include fluorinatedoil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycolesters in which the ester group contains from three to twelve carbonatoms or more, and particularly neopentyl glycol propionates, neopentylglycol butyrates,.

neopentyl glycol caproates, neopentyl glycol caprylates, neopentylglycol pelargonates, etc., (2) trimethylol alkanes such as trimethylolethane, trimethylol propane, trimethylol butane, trimethylol pentane,trimethylol hexane, trimethylol heptane, trimethylol octane, trimethyloldecane, trimethylol undecane, trimethylol dodecane, etc., as Well as theesters thereof and particularly triesters in which the ester portionseach contain from three to twelve carbon atoms and may be selected fromthose hereinbefore specifically set forth in connection with thediscussion of the neopentyl glycol esters, and (3) tricresylphosphate,trioctylphosphate, trinonylphosphate, tridecylphosphate, as well asmixed aryl and alkyl phosphates, etc.

The present invention also is used in the stabilization of greases madeby compositing one or more thickening agents with an oil of natural orsynthetic origin. Metal base synthetic greases are further classified aslithium grease, sodium grease, calcium grease, barium grease, strontiumgrease, aluminum grease, etc. These greases are solid or semi-solid gelsand, in general, are prepared by the addition to the lubricating oil ofhydrocarbon soluble metal soaps or salts of higher fatty acids as, forexample, lithium stearate, calcium stearate, aluminum naphthenate, etc.The grease may contain one or more thickening agents such as silica,carbon black, talc, organic modified bentonite, etc., polyacrylates,amides, polyamides, aryl ureas, methyl N-n-octadecyl terephthalomatc,etc. Another type of grease is prepared from oxidized petroleum wax, towhich the saponifiable base is combined with the proper amount of thedesired saponifying agent, and the resultant mixture is processed toproduce a grease. Other types of greases in which the features of thepresent invention are grease, wool grease, etc., and those made fromfats, tallow, butchers waste, etc.

Oils of lubricating viscosity also are used as transmission fluids,hydraulic fluids, industrial fluids, etc.,

used to further During such use the of the oil are important. Anysuitimprove the properties of these oils. lubricity properties ablelubricating oil which is used for this purpose is improved byincorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rollingoils, soluble oils, drawing compounds, etc. In this application, the oilis used as such or as an emulsion with water. Here again, it is desiredthat the oil serves to lubricate the metal parts of saws, knives,blades, rollers, etc., in addition to dissipating the heat created bythe contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils. Theslushing oils are employed to protect finished or unfinished metalarticles during storage or transportation from one area to another. Themetal articles may be of any shape or form including steel sheets,plates, panels, coils, bars, etc., which may comprise machine parts,engines, drums, piston rings, light arms, etc., as well as farmmachinery, marine equipment, parts for military or other vehicles,household equipment, factory equipment, etc. A coating which may bevisible to the eye, or not, as desired, covers the metal part andprotects it from corrosion, etc.

While the reaction product of the present invention is particularlyadvantageous in substrates subjected to high temperatures, it isunderstood that it may be used in other substrates which deteriorate instorage, during treatment and/ or in use. These other substrates includemotor fuels such as unsaturated gasoline, blends of unsaturated andsaturated g'asolines, etc., jet fuel, diesel oil, fuel oil, residualoil, drying oil, rubber, polyolefins, resins, waxes, etc.

The reaction product of the present invention is used as an additive inlubricating oil in a small but stabilizing concentration. Depending uponthe particular use, the additive may be employed in a concentration offrom about 0.01% to about 25% and preferably from about 0.05% to about10% by weight of the oil. These and the following concentrations are onthe basis of the active constituent 'and do not include the solvent orsolubilizing phenol when used. When used in a conventional lubricatingoil, the additive generally is employed in a concentration of from about0.01% to about 2% by weight of the oil. When used in lubricating oil formore severe opera tions, such as hypoid gear oil, the additive is usedin a concentration of from about 1% to about 20% or more by weight ofthe oil. In general, substantially the same range of additiveconcentration is employed when the oil is used as transmission fluid,hydraulic fluid, industrial fluid, etc. When the oil is used in theformulation of a grease, the additive is used in a concentration of fromabout 0.5% to about 5% by weight of the oil. When used in cutting oil,rolling oil, soluble oil, drawing compound, etc., the additive may beused in a concentration of from about 0.1% to about by weight of theoil. When used in slushing oil, the additive may be used in aconcentration of from about 0.1% to about by Weight or more of the oil.

It is understood that the additive may be used along with otheradditives incorporated in the oil for specific purposes. In most cases,it is desirable to also incorporate an antioxidant in the oil. Preferredantioxidants are of the phenolic type and include tertiarybutylcatechol, 2,6 ditertiarybutyl-4-methylphenol, 2,4-dimethyl-6-tertiarybutylphenol, etc., 2-tertiarybutyl-4-methoxyphen01,2-tertiarybutyl-4ethoxyphenol, etc. Also, other additives incorporatedin lubricating oil include metal deactivator, dye, viscosity indeximprover, pour point depressor, antifoaming additive, detergent, etc.

The followng examples are introduced to illustrate further the noveltyand utility of the persent invention but not with the intention ofunduly limiting the same.

Example I The product of this example was prepared by the reaction of Aanhydride (5,6,7,8,9,9-hexachloro-1,2,3,

,ing 213 g. (0.5 mole) of A 4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride) withdiethylenetriarnine and then reacting with mixed monoand ditridecyl acidorthophosphates. The first reaction was effected by graduallyaddanhydride to 258 g. (2.5 moles) of diethylentriarnine over a one hourperiod. Following this, 200 ml. of benzene was added and the mixture washeated and refluxed for about 1.5 hours. Approximately 9 ml. of waterwas removed during the refluxing. The benzene was removed bydistillation on a steam bath. Excess diethylenetriarnine was removed bydistillation under high vacuum. At this point, the reaction mixture wasa yellow-orange brittle solid having a basic nitrogen equivalent weightof 220 g. The product was ground to a fine powder and washed severaltimes with water, dissolved in methanol and dried with anhydrous sodiumsulfate. This was followed by filtering and evaporation of the methanol,to leave a red viscous clear liquid which crystallized to a red solidupon standing. The product had a basic nitrogen equivalent weight of 262g. This corresponds to a theoretical nitrogen equivalent of 255 for theequal mole reaction product which, as hereinbefore set forth, it isbelieved to be an imide-amine.

The reaction product of A anhydride and diethylenetriarnine, prepared inthe above manner, then was reacted with mixed monoand ditridecyl acidorthophosphates by intimately mixing at room temperature 2.55 g. (0.01equivalents) of the A anhydride-diethylenetriamine reaction product with3.73 g. (0.01 equivalent) of mixed monoand ditridecyl acidorthophosphate. The mixture was warmed and stirred until homogeneous.Upon cooling the product was recovered as a brown clear waxy solid.

Example 11 The composition of this example is a phosphate prepared fromanother portion of the A anhydride-diethylenetriarnine reaction productdescribed in Example I. The phosphate used in this example is apolyoxyethylenated nonylphenol phosphate containing an average of aboutfive oxyethylenated groups. The polyoxyethylenated nonylphenol phosphatewas prepared in the manner hereinbefore described. The salt was preparedby mixing at room temperature, with intimate stirring, 5.12 g. (4equivalents) of the A anhydride-diethylenetriarnine reaction productwith 22.4 g. (4-equivalents) of the polyoxyethylenated nonylphenolphosphate. The product was recovered as a brown cle'ar viscous liquidand, upon analysis, was found to have a refractive index n of 1.508 anda Gardner Vertical Viscosity at 60 C. of 22 sec.

Example 111 Example IV The composition of this example is thepolyoxyethylenated nonylphenol dithiophosphate salt prepared fromahother portion of the A anhydride-diethylenetriamine reaction productdescribed in Example I. The polyoxyethylenated nonylphenoldithiophosphate is prepared in the manner hereinbefore described. Thesalt is prepared by admixing equivalent proportions of the reactants atroom temperature with intimate mixing.

portion of A acid at ing equal mole proportions of The composition ofthis example is the mixed monoand dioctyl acid orthophosphate salts ofthe mono salt prepared by the reaction of equal mole proportions of Aacid and Duomeen T. As hereinbefore set forth, Duomeen T isN-alkyl-l,3-diaminopropane in which the alkyl group contains from twelveto twenty carbon atoms and mostly sixteen to eighteen carbon atoms. TheA acid and Duomeen T are admixed in equal mole proportions at roomtemperature with intimate stirring. For ease in handling and reaction,the A acid is prepared as a solution in benzene and the Duomeen T isadded thereto. Following completion of the reaction, the solvent isremoved from the mixture and the mono salt is recovered as a viscousmaterial. To this product is added an equivalent proportion of the mixedmonoand dioctyl acid orthophosphates and intimately stirred at roomtemperature until completion of the reaction.

Example VI The double dithiophosphate salt of the reaction prodnot of Aacid and Duomeen T is prepared by reacting two mole proportions ofDuomeen T with one mole proroom temperature with intimate stirring. Hereagain, the reaction conveniently is effected in benzene solvent. Thedouble salt is recovered in the solvent and to this is added twoequivalents of the mixed monoand didecyl dithiophosphates per oneequivalent of the double salt of A acid and Duomeen T. The salt isprepared by intimately mixing the reactants at room temperature.

Example VII The composition of this example is prepared by reactingequal mole proportions of B anhydride (5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-octahydro 1,4,5,8dimethano-2,3-naphthalenedicarboxylic anhydride) and Diam 26. Ashereinbefore set forth, Diam 26 is substantially the same as Duomeen T.This reaction is effected by refluxing the B anhydride and Diam 26 inbenzene solvent, with the concomitant removal of water formed during thereaction. Following completion of the reaction, an equivalent proportionof polyoxyethylenated nonylphenol phosphate containing an average ofabout five polyoxyethylenated groups is commingled with the Banhydride-Diam 26 reaction mixture. The resulting mixture is stirred atroom temperature for a sufiicient time to efiect salt formation.

Example VIII The composition of this example is prepared by reactingequal mole proportions of HET acid (1,4,5,6,7,7- hexachlorodicyclo(2.2.1)--heptene 2,3-dicarboxylic acid) and Duomeen T. The reaction isconveniently effected in the presence of ethyl ether solvent and thereaction mixture is intimately stirred at room temperature untilcompletion of the reaction. To the reaction mixture there is added anequivalent proportion of dodecyl thiophosphate and then is stirred atroom temperature until salt formation is efiected.

Example IX The composition of this example is prepared by react- Banhydride and N,N'-disecoctyl-pphenylenediamine under refluxingconditions 14 in the presence of benzene solvent. Following completionof the reaction, an equivalent proportion of polyoxypropylenateddinonylphenol phosphate containing an average of four oxypropylenegroups is added to the amide-amine mixture and is stirred intimately atroom temperature until salt formation is effected.

Example XI As hereinbefore set forth, the salt of the present inventionis conveniently prepared in solution for use as an additive. When thesalt is to be used as an additive in a g oil such as, for example,dioctyl sebacate, marketed commercially under the trade name of Plexol201, the salt conveniently is prepared as a stock solution in thissynthetic oil. Such an additive composition was prepared by comminglingat room temperature and intimately mixing 2.55 g. of the Aanhydridediethylenetriamine reaction product, prepared as described inExample I, 3.73 g. of mixed monoand dimdecyl acid orthophosphates and6.28 g. of dioctyl sebacate. The resultant mixture is a viscous amberliquid solution.

Example XII Another composition similar to that described in Example IIwas prepared in admixture with dioctyl sebacate as follows: 1.28 g. ofthe A anhydride-diethylenetriamine reaction product prepared ExampleXIII Example XIV The composition of this example was prepared by commingling 2.55 g. of the A anhydnide-diethylenetriamine perature andtheproduct was recovered as a. viscous liquid.

Example XV As hereinbefore set forth, the salt of the present inventionis of especial utility in substrates encountering high temperaturesduring use. An example of such a substrate is lubricating oil andespecially such oils used in the lubrication of hypoid gears which mustmeet severe requirements of high torque-low speed, 10w torque-high speedand high torque-high speed conditions. The requirements are even moresevere because such oils must retain their lubricity properties for longperiods of time as exemplified, for example, by the recommendations ofnot changing oil for one year or more or 20,000 miles or more ofoperation and even up to 100,000 miles or for the life of the vehicle.

One method of evaluating E.P. (extreme pressure) lubricat ing oils is bythe Falex machine. This procedure is described in detail in a bookentitled Lubricant Testing authored by E. G. Ellis and published byScientific Publications (Great Britain) Limited, 1953, pages 154.Briefly, the Falex machine consists: of a rotating pin which runsbetween two V shaped bearings which are spring loaded against the pinand provided with means for varying the load. The oil to be tested ispoured into a metal trough in which the pin and bearings are partlysubmerged. The machine was operated for ,5 minutes each at 250 and 500pound loads and then 45 minutes at 750 pound load. The data collectedincludes the temperature of the oil at each of the loads and the torquein pounds per square inch at each load, as well as the wear which isdetermined by a ratchet wheel arrangement in which the teeth areadvanced in order to maintain the desired load. Each tooth is equivalentto approximately 0.000022 inch. Preferred additives are those whichimpart low temperature, low torque and low wear to the oil.

In another series of tests the machine was operated for minutes at eachload from 250 pounds to seizure at 250 pound increments. The maximumload and the time in minutes at this load to seizure are reported, aswell as the temperature of the oil. In this case the higher temperatureis preferred because it means that the oil is operating satisfactorilyat a higher temperatur The lubricating oil used in this example isdioctyl sebacate synthetic lubricating oil marketed under the trade nameof Plexol 201 R-un No. l in the following Table I is a run made usingthe Plexol not containing an additive and thus is the blank or controlrun.

Run No. 2 is a run made using another sample of the Plexol to which hasbeen added 2% by weight of the salt prepared as described in Example XI.

Run No. 3 is a run made using another sample of the Plexol to which hadbeen added 2% by weight of the salt prepared as described in ExampleXII.

Run No. 4 is a run made using another sample of the Plexol to which hadbeen added 2% by weight of the salt prepared as described in ExampleXIII.

Run No. 5 is a run made using another sample of the Plexol to which hasbeen added 2% by weight of the salt prepared as described in ExampleXIV.

From the data in the above table, it will be seen that the dioctylsebacate without additive (Run No. 1) underwent seizure at a load of 750pounds. In contrast, seizure conditions for the samples of the dioctylsebacate containing the additives of the present invention were 1500 and1750 pounds. Also of importance is the fact that the oil after test inRun No. 3 was clear, thus demonstrating that the additive served toavoid darkening of the oil during the severe test conditions Similarly,the oil in Run No. 2 underwent only little darkening during theevaluation.

Example XVI Another series of evaluations were made using a puri- 1. 6Company as Games 340 White Oil." tions of this oil include thefollowing:

Typical specifica- Distillation range, F. 740-975 Specific gravity at F0.8836 Viscosity:

At F. 360

At 210 F 52.2 Flash point, COC, F 440 Pour Point, F -20 Refractive indexat 68 F 1.4805 Saybolt color +30 II is the run made additive and thus isRun No. 6 in the following Table using the white oil not containing anthe blank or control run.

Run No. 7 is a run made using another sample of the white oil to whichhad been added 2% by weight of the additive prepared as described inExample XI.

Run No. 8 is a run made using another sample of the white oil to whichhad been added 2% by weight of the additive prepared as described inExample XII. The salt was not readily soluble in the white oil andaccordingly was solubilized by commingling nonylphenol therewith andheating and stirring as required.

Run No. 9 is a run made using another sample of the white oil to whichhad been added 2% by weight of the additive prepared as described inExample XIII Here again, the salt was solubilized with nonylphenol.

Run No. 9 is a run made using another sample of the the white oil towhich had been added 2% by weight of the additive prepared as describedin Example XIV. Here again, the salt was solubilized with nonylphenol.

Here again, it will be seen that the oil without additive (Run No. 6)underwent seizure by the time the load had increased to 425 pounds. Incontrast, the white oil containing the additive of the present inventiondid not undergo seizure until loads of 1250 and 1500 pounds.- Also ofimportance is the fact that the white oil in Run N0. 8, after exposureto the severe conditions, was clear. The oils in Runs No. 7 and 9 haddarkened only slightly.

Example XVII The reaction product of Example I is used in aconcentration of 0.3% by weight as an additive in grease. The additiveis incorporated in a commercial Mid-Continent lubricating oil having anS.A.E. viscosity of 20. Approximately 92% of the lubricating oil then ismixed with approximately 8% by weight of lithium stearate.

fied mineral oil marketed commercially by A. H. Games 50 The mixture isheated to about 232 C., with constant TABLE I Temperature, F. Torque,lbs. Wear, Teeth Seizure Conditions 500 750 250 500 750 250 500 750 LoadTime Temperature, F.

231 1 490 3-4 9-10 1 l8 0 0 750 2 490 177 285 378 5-7 14-17 18-23 0 0 91, 750 0. 1 536 243 343 5-7 12-13 17-20 0 0 5 l, 500 I. 6 525 21 4-511-14 14-19 0 0 9 1, 500 1. 7 625 0 0 19 1, 750 1. 7 700 l Seizure.

TABLE 11 Temperature, F. 'Iorque,lbs. Wear, Teeth Seizure Conditions 250500 750 250 500 750 250 500 750 Load Time Temperature, F.

17 agitation. Subsequently the grease is cooled, while agitating, toapproximately 120 C., and then the grease is further cooled slowly toroom temperature.

The stability of the grease is tested in accordance with ASTM D942method, in which method a sample of the grease is placed in a bomb andmaintained at a temperature of 120 C. Oxygen is charged to the bomb, andthe time required for a drop of pounds pressure is taken as theInduction Period. A sample of the grease without additive will reach theInduction Period in about 8 hours. On the other hand, a sample of thegrease containing 0.3% by weight of the additive of the presentinvention will not reach the Induction Period for more than 100 hours.

Example XVIII In another embodiment the reaction products of the presentinvention possess insecticidal properties with good inner-therapeuticaction. They may be employed against many types of mites and insectssuch as, for example, Corausius larvae, Cotoneaster aphid, apple aphid,

black bean aphid, aster aphid, green peach aphid, chrys-- anthemumaphid, pea aphid, etc. The reaction products or mixture of these may beused for the control of various larvae, mites, eggs of mites and suchinsects as flour beetle, mexican bean beetle, black carpet beetle,milkbeetle, Mexican bean beetle, black carpet beetle, milkweed bug,German cockroaches, southern army worms, mealy bug, sow bug, citrus redspider, greenhouse red spider, various mosquitoes, yellow fevermosquito, malarial mosquito houseflies, etc.

As an example, an insecticidal composition is prepared by dissolving 1g. of the reaction product of Example I in 2 cc. of benzene andemulsifying the resultant solution with 110 cc. of Water using TritonX-l00 as the emulsifying agent. The resulting emulsion is sprayed into acage containing houseflies and results in greater than 98% knockdown.

Example XIX Example I describes the use of phosphate salt of amideamineprepared from the anhydride and amine. Example V describes a phosphatesalt of the mono salt of acid and amine and Example VI describes aphosphate prepared from the double salt of acid and amine; In anotherembodiment the phosphate salt is prepared of an amide-amine which, inturn, is prepared from the anhydride and a polyamine containing primaryand/or secondary amines. When the anhydride and the amine are mixed atroom temperature, with the resultant exothermic reaction occurring, itis believed that the anhyride structure is broken and one hydrogen ofthe amine attaches to the oxygen to torm a carboxyl group and thenitrogen of the amine attaches to the other carbon atom, therebyresulting in an amide. Accordingly, when HET anhydride, A anhydride, Banhydride, etc., is reacted at room temperature with an alkylenepolyamine, an N-alkylalkylene-polyamine or anN,N'-dialkylalkylene-polyamine, these being selected from thosehereinbefore specifically set forth, an amide-amine is formed. It isunderstood that a mixture of products including inner salts, etc., alsopreferably are formed. As a specific example, A anhydride is mixed atroom temperature with N,N-di-secotyl-ethylenediamine and the mixture isintimately stirred. In this example, the mixture is not subjected torefluxing which, when a primary amine is used, will result in theimide-arnine heretofore described. The reaction product of the acid andamine then is mixed with an equal equivalent of mixed monoanddietridecyl acid ortho-phosphates to form the phosphate salt.

We claim as our invention:

1. An organic substrate subject to deterioration during storage,transportation and use containing, as an inhibitor against saiddeterioration, a small but stabilizing concentration of the phosphatesalt of the reaction product of compound (a) and compound (b) formed byreaction of said compounds at a temperature of from about 10 to about250 C. in a proportion of from one mole of compound (a) with from one totwo moles 'of compound (b), said compound (b) being selected from thegroup consisting of:

(1) alkylene polyamine having from 2 to 4 nitrogen atoms per moleculeand containing from 2 to 6 carbon atoms per alkylene group,

(2) alkylene polyamine having from 2 to 4 nitrogen atoms per moleculeand containing from 2 to 6 carbon atoms per alkylene group and having onat least one of the nitrogen atoms an alkyl of from 1 to 20 carbonatoms,

(3) N-alkyldiaminoalkane in which the alkyl contains from about 8 toabout 25 carbon atoms and the alkane moiety contains from 2 to 6 carbonatoms,

(4) ortho-, metaand para-phenylenediamine,

(5) N-alkyl and N,N'-dialkyl phenylenediamine in which each alkylcontains from 1 to about 12 carbon atoms,

(6) diaminodiphenyl alkane containing from 1 to about 6 carbon atoms inthe alkane moiety, and

(7) diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenylamine and said diaminodiphenyl compounds having on at least one of thenitrogen atoms an alkyl of from 1 to about 16 carbon atoms,

and said compounds (a) being selected from the group consisting ofpolyhalopolyhydropolycyclicdicarboxylic acid and correspondinganhydride, said acid having the formula:

in which X is chlorine, bromine, hydrogen or alkyl of from 1 to 10carbon atoms, at least two of the Xs being chlorine or bromine, Y ischlorine, bromine, hydrogen or alkyl of l to 10 carbon atoms, m is aninteger of from 1 to 4, n ranges from 0 to 4, and p ranges from 0 to 4,said phosphate salt being formed by the reaction at a temperature offrom ambient to about 70 C. of one mole proportion of said reactionproduct of compound (a) and compound (b) with from about 0.5 to about 4mole proportions of a phosphorus compound selected from the groupconsisting of (1) phosphoric acid,

(2) alkyl phosphate and alkyl thiophosphate containing alkyl of trom 1to about 20 carbon atoms,

(3) phosphate and dithiophosp'hate of oxyalkylenated aliphatic alcoholcontaining from 4- to 20 carbon atoms and from 1 to 12 oxya-lkylenegroups of from 2 to 6 carbon atoms,

(4) phosphate and dithiophosphate of oxyalkylenated phenol containingfrom 1 to 12 oxyalkylene groups of from 2 to 6 carbon atoms, and

(5) phosphate and dithiophosphate of oxyalkylenated alkyl phenolcontaining from 1 to 3 alkyls of from 1 to 20 carbon atoms each andcontaining from 1 to 12 oxyalkylene groups of from 2 to 6 carbon atoms.

2. The composition of claim 1 wherein said organic substrate is alubricant comprising a major portion of an oil of lubricating viscosity.

3. The composition of claim 1 wherein said organic substrate compriseslubricating oil.

4. The composition of claim 1 wherein said organic substrate comprisesgrease.

5. The composition of claim 1 wherein said compound 19 (a) is5,6,7,8,9,9 hexachloro-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2-3-naphthalenedicanboxylic anhydride.

6. The composition of claim 1 wherein said compound (a) is 5,6,7,8,9,9hexachloro 1,2,3,4,4a,5,8,8aoctahydro 1,4,5,8 dimethano 2,3,naphthalenedicarboxylic anhydride.

7. -The composition of claim 1 wherein said compound (a) is1,4,5,6,7,7,-hexachlorodicyclo-(2.2.1)-5-heptene- 2,3-dicarboxylic acid.

8. The composition of claim 1 wherein said compound (b) isN-alkyl-diaminoal'kane containing from about eight to about twenty-fivecarbon atoms in the alkyl group and from two to six carbon atoms in thea-Ikane moiety.

9. The composition of claim 1 wherein said reaction product of compound(a) and compound (lb) is reacted with a mixture of monoand dialkylphosphates containing from about six to about twenty carbon atoms in thealkyl groups.

,110. The composition of claim 1 whereinv said reaction product ofcompound (a) and compound (b) is reacted with a mixture of monoanddialkyl dithiophosphates containing from about six to about twentycarbon atoms in the alkyl groups.

References Cited by the Examiner UNITED STATES PATENTS 2,622,096 12/1952Ladd 252-49.9 X 2,963,435 12/1960 Fields 25246.7 2,970,110 1/1961 Fields252-467 X 3,184,412 5/1965 Lowe et al. 25232.7 X 3,185,645 5/1965Clayton 252-32.7 X 3,208,939 9/1965 Latos et al. 44-63 X DANIEL E.WYMAN, Primary Exwminer. P. P. GARVIN, Assistant Examiner.

1. AN ORGANIC SUBSTRATE SUBJECT TO DETERIORATION DURING STORAGE,TRANSPORTATION AND USE CONTAINING, AS AN INHIBITOR AGAINST SAIDDETERIORATION, A SMALL BUT STABILIZING CONCENTRATION OF THE PHOSPHATESALT OF THE REACTION PRODUCT OF COMPOUND (A) AND COMPOUND (B) FORMED BYREACTION OF SAID COMPOUNDS AT A TEMPERATURE OF FROM ABOUT 10* TO ABOUT250*C. IN A PROPORTION OF FROM ONE MOLE OF COMPOUND (A) WITH FROM ONE TOTWO MOLES OF COMPOUND (B), SAID COMPOUND (B) BEING SELECTED FROM THEGROUP CONSISTING OF: (1) ALKYLENE POLYAMINE HAVING FROM 2 TO 4 NITROGENATOMS PER MOLECULE AND CONTAINING FROM 2 TO 6 CARBON ATOMS PER ALKYLENEGROUP, (2) ALKYLENE POLYAMINE HAVING FROM 2 TO 4 NITROGEN ATOMS PERMOLECULE AND CONTAINING FROM 2 TO 6 CARBON ATOMS PER ALKYLENE GROUP ANDHAVING ON AT LEAST ONE OF THE NITROGEN ATOMS AN ALKYL OF FROM 1 TO 20CARBON ATOMS, (3) N-ALKYLDIAMINOALKANE IN WHICH THE ALKYL CONTAINS FROMABOUT 8 TO ABOUT 25 CARBON ATOMS AND THE ALKANE MOIETY CONTAINS FROM 2TO 6 CARBON ATOMS, (4) ORTHO-, META- AND PARA-PHENYLENEDIAMINE, (5)N-ALKYL AND N,N''-DALKYL PHENYLENEDIAMINE IN WHICH EACH ALKYL CONTAINSFROM 1 TO ABOUT 12 CARBON ATOMS, (6) DIAMINODIPHENYL ALKANE CONTAININGFROM 1 TO ABOUT 6 CARBON ATOMS IN THE ALKANE MOIETY, AND (7)DIAMINODIPHENYL ETHER, DIAMINODIPHENYL SULFIDE, DIAMINODIPHENYL AMINEAND SAID DIAMINODIPHENYL COMPOUNDS HAVING ON AT LEAST ONE OF THENITROGEN ATOMS AN ALKYL OF FROM 1 TO ABOU 16 CARBON ATOMS, AND SAIDCOMPOUNDS (A) BEING SELECTED FROM THE GROUP CONSISTING OFPOLYHALOPOLYHYDROPOLYCYCLICDICARBOXYLIC ACID AND CORRESPONDINGANHYDRIDE, SAID ACID HAVING THE FORMULA: